The hybrid metal–organic framework [(CH3)2NH2]Fe(HCOO)3with a perovskite-like structure exhibits a variety of unusual magnetic behaviors at low temperatures. While the long-distance super-exchange through the Fe-O–CH-O–Fe exchange path leads to a canted antiferromagnetic ordering at TN～ 19 K, a second transition of magnetic blocking develops at TB～ 9 K. The stair-shaped magnetization hysteresis loops below TBresemble the behaviors of resonant quantum tunneling of magnetization in single-molecular quantum magnets. Moreover, the magnetic relaxation also exhibits several features of resonant quantum relaxation, such as the exponential law with a single characteristic relaxation time, and the nonmonotonic dependence of relaxation rate on the applied magnetic field with a much faster relaxation around the resonant fields. The origin of quantum tunneling behaviors in the [(CH3)2NH2]Fe(HCOO)3metal–organic framework is discussed in terms of magnetic phase separation due to the modification of hydrogen bonding on the long-distance super-exchange interaction. The hybrid metal-organic framework [(CH3) 2NH2] Fe (HCOO) 3with a perovskite-like structure exhibits a variety of unusual magnetic behaviors at low temperatures. While the long-distance super-exchange through the Fe-O-CH-O -Fe exchange path leads to a canted antiferromagnetic ordering at TN ~ 19 K, a second transition of magnetic blocking develops at TB ~ 9 K. The stair-shaped magnetization hysteresis loops below TBresemble the behaviors of resonant quantum tunneling of magnetization in single-molecular quantum magnets. Moreover, the magnetic relaxation also exhibits several features of resonant quantum relaxation, such as the exponential law with a single characteristic relaxation time, and the nonmonotonic dependence of relaxation rate on the applied magnetic field with a much faster relaxation around the resonant fields . The origin of quantum tunneling behaviors in the [(CH3) 2NH2] Fe (HCOO) 3metal-organic framework is discussed in terms of magnetic phase separation due to the modi fication of hydrogen bonding on the long-distance super-exchange interaction.